Pyrazole azo dyestuffs containing a sulfonylurea or sulfonylurethane substituent

ABSTRACT

Pyrazole azo dyestuffs of the formula:   WHEREIN D is an optionally substituted phenyl group, X1 is -OH or -NH2, X is an oxygen atom or an optionally substituted, nitrogen atom R is hydrogen, alkyl, or aryl, R2 is aryl, and WHEREIN THE PRYAZOLE RING MAY BE OPTIONALLY SUBSTITUTED IN THE 3-POSITION. The dyestuffs of this invention are free of sulfonic acid groups and are sparingly soluble or insoluble in water. The dyestuffs are especially useful for dyeing and printing synthetic fibers particularly polyester fibers in fast yellow shades with excellent fastness to light, and to sublimation.

United States Patent [191 Desai et al.

[ 51 Oct. 22, 1974 PYRAZOLE AZO DYESTUFFS CONTAINING A SULFONYLUREA ()R SULFONYLURETHANE SUBSTITUENT [75] Inventors: Nalin Binduprasad Desai; Onnusami Jayaraman, both of Goregaon-Bombay, India, Visvanathan Ramanthan, Basel; Klaus Artz, Muttenz, both of Switzerland; Navnitrai Nagarji Naik, Goregaon-Bombay, India; Walter Jenny, Basel, Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: Dec. 15, 1971 [21] App]. No: 208,464

Related U.S. Application Data [63] Continuation-impart of Ser. No. 806,291, March 11,

1969, Pitt. N0. 3,679,657.

[30] Foreign Application Priority Data Mar. 18, 1968 Switzerland 3958/68 [52] U.S. Cl 260/163, 260/158, 260/165, 260/186, 260/202, 260/207, 260/207.l, 260/282, 260/372, 260/376, 260/377,

260/545 R, 260/556AR, 260/556 AB [51] Int. CL... C09b 29/36, C09b 29/38, D06p 3/52 [58] Field of Search 260/162, 163

[56] References Cited UNITED STATES PATENTS 2,799,673 7/1957 Bolliger 260/163 Mueller et al, 260/l58 X 3,324,105 6/1967 Hanke et al. 260/158 3,366,620 1/1968 Hanke et al. 260/l63 3,379,713 4/1968 Wallace et al 260/158 3,544,548 12/1970 Giinther et a] 260/152 Primary ExaminerFloyd D. Higel Attorney, Agent, or Firm-loseph G. Kolodny; Edward McC. Roberts; Prabodh l. Almaula [57] ABSTRACT Pyrazole azo dyestuffs of the formula:

l (alkylene or phenylene)-XCON RS 0 R;

groups and are sparingly soluble or insoluble in water.

The dyestuffs are especially useful for dyeing and printing synthetic fibers particularly polyester fibers in fast yellow shades with excellent fastness to light, and to sublimation.

2 Claims, No Drawings PYRAZOLE AZO DYESTUFFS CONTAINING A SULFONYLUREA OR SULFONYLURETHANE SUBSTITUENT This application is a continuation-in-part of U.S. Ser.

No. 806,291, filed Mar. ll, 1969, now U.S. Pat. No.

methyl, ethyl, propyl or benzyl groups.

The invention for example relates to azo dyestuffs, especially monoazo dyestuffs and disazo dyestuffs, anthraquinones, perinones, quinphthalones, styryl dyestuffs and nitro dyestuffs.

Azo dyestuffs The particularly interesting dyestuffs include the monoazo dyestuffs of formula D-N=NA--NR,R wherein D is the residue of a diazo component, A is an arylene residue, especially an optionally substituted 1,4-phenylene residue, R, and R are each an optionally substituted alkyl group, with at least one of the residues D, A, R, and R containing a group of formula -X-CO-NR--SO R wherein R is a monovalent residue, especially an aliphatic a cycloaliphatic, araliphatic, aromatic or heterocyclic residue, such as for example a methyl, ethyl, n-propyl, n-butyl, cyclohexyl, p-tolyl, 2,5-dimethylphenyl, 4-(chloro, fluoro or bromo)phenyl, benzthiazole-Z, pyridyl or thienyl-2 residue.

The diazo residue D is mainly derived from monocyclic or bicyclic amines of formula D-NH such as any desired diazotisable heterocyclic amines which do not contain any acid substituents conferring solubility in water, but especially from amines which possess a heterocyclic five-membered ring with two or three heteroatoms, above all a nitrogen atom and one or two sulphur, oxygen or nitrogen atoms as hetero-atoms, and aminobenzenes, especially those of formula wherein a denotes a hydrogen or halogen atom, or an alkyl or alkoxy, nitro, nitrile, carbalkoxy or alkylsulphone group, b denotes a hydrogen or halogen atom, or an alkyl, nitrile or trifluoromethyl group, c denotes 3 nitro, nitrile, carbalkoxy, aryl or alkylsulphenyl group and d denotes a hydrogen atom, a halogen atom, a carboxylic acid ester group or a carboxylic acid amide group.

The following may be mentioned as examples: 2- aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5- methylsulphonylthiazole, 2-amino-5-cyanothiazole, 2- amino-4methyl-S-nitrothiazole, 2-amino-4- methylthiazole, 2-amino-4-phenylthiazole, 2-amino-4- 4'-chloro)-phenylthiazole, 2-amino-4-( 4'-nitro)- 2 phenylthiazole, B-aminopyridine, 3-aminoquinoline, 3-aminopyrazole, 3-aminol -plhenylpyrazole, 3- aminoindazole, 3-aminol ,2,4-triazole, 5-( methyl, ethyl, phenyl or benzyl)-l,2,4-triazole, 3-amino-l-( 4- methoxyphenyl)-pyrazole, Z-aminobenzthiazolc, 2-amino-6-methylbenzthiazole, 2-amino-6- methoxybenzthiazole, 2-amino-6-chlorobenzthiazole, 2-amino-6-cyanobenzthiazole, 2amino-6- thiocyanatobenzthiazole, 2-amino-6-nitrobenzthiazole, 2-amino-6-carbethoxybenzthiazole, 2-amino-(4- or 6- )methylsulphonylbenzthiazole, Z-aminol ,3 ,4- thiadiazole, 2-amino-l,3,5-thiadiazole, 2-amino-4- phenyl or 4-methyl-l,3,5-thiadliazole, 2-amino-5- phenyl-l ,3,4-thiadiazole, 2-amino-3-nitro-5-methylsulpho-thiophene, 2-amino-3,5-bis-( methylsulpho)- thiophene, 5-amino-3-methyl-isothiazole, 2-amino-4- cyano-pyrazole, 2-( 4 -nitrophenyl)-3-amino-4- cyanopyrazole, 3- or 4-aminophthalimide, aminobenzene, l-amino-4-chlorobenze:ne, l-amino-4 bromobenzene, l-amino-4-methylbenzene, l-amino-4- nitrobenzene, l-amino-4-cyanobenzene, l-amino-2,5- dicyanobenzene, l-amino-4-methylsulphonylbenzene, l-amino-4-carbalkoxybenzene, l-amino-2,4-

dichlorobenzene, l-amino-2,S-dichlorobenzene, l-amino-2,4-dibromobenzene, l-amino-2 -methyl-4- chlorobenzene, l-amino-2-trifluoromethyl-4- chlorobenzene, l-amino-2-cyano-4-chlorobenzene, lamino-2-carbomethoxy-4-chlorobenzene, l-amino-2- carbomethoxy-4-nitrobenzene, l-amino-2-chloro-4 cyanobenzene, l-amino-2-chloro-4-nitrobenzene, lamino-2-bromo-4-nitrobenzene, l-amino-2-chloro-4- carbethoxybenzene, I-amino-2-chloro-4-methylsulphonylbenzene, l-amino-2-methylsulphonyl-4 -chlorobenzene, l-amino2-methylsulphonyl-4-nitrobenzcne, l-amino-2,4-dinitrobenzene, l-amino-2,4- dicyanobenzene, l-amino-2-cyano-4-methylsulphonylbenzene, l-amino-2,6-dichloro-4-cyanobenzene, lamino-2,6-dichloro-4-nltrobenzene, l-amino-2,4- dicyano-6-chlorobenzene, 4-aminobenzoic acid cyclohexyl ester, l-amino-2,4-dinitro--chlorobenzene and especially l-amino-2-cyano-4-nitrobenzene, and also l-aminobenzene-2-, -3- or -4-sulphonic acid amides, such as the N-methylamide or N,N-dimethylamide or N,N-diethylamide.

Diazo components of formula wherein a, b or c' denote a residue of formula X- CO-NRSO R should be mentioned particularly.

The group A is preferably the residue of formula wherein c and d are hydrogen atoms or methyl, ethyl, methoxy, ethoxy, phenylthio or plienoxy residues.

The group c is preferably bonded in the orthoposition to the azo group and can, in addition to the above-mentioned groups, also denote a chlorine or bro mine atom, a trifluoromethyl group, an alkylsulphonyl group, preferably a methylsulphonyl group, and an acylamino group which-is optionally alkylated, preferably methylated, at the nitrogen atom and in which the acyl a lower alkyl groups, that is to say alkyl groups containing one to four, preferably two to four, carbon atoms, such as methyl, ethyl, n-propy1 or n-butyl groups which may be substituted in the usual manner such as for example benzyl or B-phenylethyl groups, halogenated alkyl groups, such as B-chlorethyl, B,B,B-trifluorethyl, B;y-dichloropropyl, B-cyanethyl, alkoxyalkyl, such as B-ethoxyethyl or n-methoxybutyl, hydroxyalkyl, such as fl-hydroxyethyl, B;y-dihydroxypropyl, nitroalkyl, such as ,B-nitroethyl, carbalkoxy, such as ,B-carbomethoxy, ethoxy or propoxy)-ethyl with the terminal alkyl group being permitted to carry nitrile, carbalkoxy, acyloxy and amino groups in the w-position), B- or 'y-carbo-( methoxy or ethoxy)-propyl, acylaminoalkyl, such as {3-( acetyl or formyl)-aminoethyl, acyloxyalkyl, such as B-acetoxyethyl, B;y-diacetoxypropyl, B-(alkyl or aryl)-sulphonylaikyl, such as B-methanesulphonylethyl, B-ethanesulphonylethyl or B-(pchlorobenzenesulphonyl)-ethy1, alkylor my!- carbamoyloxy-alkyl, such as ,B-methylcarbamyloxyethyl and ,B-phenylcarbamyloxyethyl, alkyloxycarbonyloxyalkyl, such as ,8-( methoxy, ethoxy or isopropoxy)-carbonyloxyethyl, 'y-acetamidopropyl, B4 p-nitrophenoxy)-ethyl, ,B-( p-hydroxyphenoxy)- ethyl, B4B-acetylethoxycarbonyl)-ethyl, B-[B'-cyano, hydroxy, methoxy or acetoxy)ethoxycarbonyH-ethyl, cyanalkoxyalkyl, B-carboxyethyi, B-acetylethyl, y-aminopropyl, B-diethylaminoethyl, B-cyanacetoxyethyl and B-benzoyl-B-(p-alkoxy or phenoxybenzoyl)-oxyethyl groups,

Particularly preferably, R, and/or R denote a residue of formula alkylene-XCO-NRSO R such as for example a B-(N-phenylsulphonyl-N- methylaminocarbonyloxy)-ethyl or a 'y-( N- phenylsulphonyl-N-methylaminocarbonylamino)- propyl residue.

The groups R and R generally contain not more than 18 carbon atoms.

Another preferred type of monoazo dyestuffs has the formula R SO NR-COX-D'N=NA, wherein D is an optionally substituted p-phenylene residue and A is the residue of a coupling component such as for example a phenol, an enol, an aromatic amine or a pyrazolone, D preferably being a residue of formula V I p a l msm-nn-oo-x-Q, V7 7 .7 b 7 wherein a and b have the same significance as above.

Particularly preferred disazo dyestuffs are those of formula i wherein D, A, R, R and X have the same significance as above and R is a bivalent organic residue, especially an aliphatic, araliphatic, cycloaliphatic, aromatic or heterocyclic residue such as for example a hexamethylene-l,6- or phenylene-l,3 residue.

Further dyestuffs to be mentioned are the disazo dyestuffs of formula wherein R and R have the same significance as above, and the disazo dyestuffs of formula R -SO --NR-COXR -D'N=N--D -N=N-A' whereinR, R R D and A have the same significance as above and D is a p-phenylene residue. Referred dyestuffs have the formula D-N=)\ NPy( C -C alkylene or phenylene)X- CONR-SO R wherein D is the residue of a diazo component of the benzene series, X is O- or NR wherein R is hydrogen or C,-C -alkyl, R is C C -aryl and Py is a pyrazole residue bound in 1- position and in 4-position, the latter to the azo bridge.

Particularly valuable are the dyestuffs of the formula (a lkylene or ary1ene)X-C 0-N R-S 0 -12;

wherein M is C C -alkyl, phenyl COO(C -C.,-alkyl or phenyl), CONH optionally C C -alkylated, and X is NH or OH.

Styryl dyestuffs Preferred styryl dyestuffs are those of formula wherein A, R and R have the same significance as above and Y is a nitrile, carbalkoxy or arylsulphonyl group, such as for example a carbethoxy or phenylsulphonyl group.

Particularly interesting dyestuffs are those of formula wherein R is an alkyl group or preferably an aromatic group such as a phenyl group and R is an alkyl. or analkyl group or the residue of formula CH C- H OCON-( CH )SO R Preferred bis-styryl dyestuffs are those of formula wherein R, R R A, X and Y have the same significance as above. Anthraquinoid dyestuffs Dyestuffs according to the invention of the anthraquinone series are for example anthraquinone derivatives of formula wherein n is an integer from 1 to 4, preferably 1, X, R and R have the same significance as above and A denotes an anthraquinone residue having three or four condensed rings, which contain one or more other substituents such as for example halogen atoms such as fluorine, chlorine or bromine, hydroxyl groups, alkoxy groups, amino groups, acylamino groups, alkylamino groups having one to three carbon atoms, acyloxy groups, optionally substituted aryl residues, optionally substituted heterocyclic residues, arylamino groups, wherein the aryl residue is preferably a phenyl group which may be substituted by one or more halogen atoms, alkyl or alkoxy groups, alkylsulphonyl or optionally substituted phenylsulphonyl groups, alkylthioether or optionally substituted phenylthioether residues as well as nitro, nitrile, carboxylic acid ester and acetyl groups. Examples of tetracyclic anthraquinone residues are 1,9-isothiazolanthrone, 1,9- anthrapyrimidine or l,9-pyrazolanthrone. The alkyl residues are preferably lower alkyl residues which can contain up to six carbon atoms.

Preferred anthraquinone dyestuffs are for example those of formula wherein B denotes a halogen atom, especially a bromine or chlorine atom, or an alkyl or alkoxy group, especially methyl or methoxy, n 1 or 2 and Z Z Z and Z each denote a hydrogen atom, an amino or hydroxyl group which is optionally substituted by an alkyl, aralkyl, cycloalkyl, aryl or heterocyclic residue, or an amino or hydroxyl group substituted by an organic acid residue, with at least one of the symbols Z Z Z, or Z containing or denoting a group of formula -X- -CONRSO R such as for example a group of formlilla 0r -N(CH )--CON(CH )-SO R wherein R has the same significance as given above.

Other preferred anthraquinone dyestuffs are for example those of formula Further preferred anthraquinone dyestuffs are for ex-- ample those of formula II I 0 Z:

wherein Z Z Z 2,, B, n, X, R and R have the same significance as above, A is an aliphatic, araliphatic, aromatic or heterocyclic residue which is optionally interrupted or substituted by hetero-atoms, and X is a direct bond, a sulphonyl, sulphonyloxy or sulphonylamino group or has the same significance. as given for X. Amongst these dyestuffs, the subgroup wherein the symbol X is a direct bond, the symbol Hal is a chlorine or bromine atom, the group X is an oxygen atom and the group R is a lower alkyl residue or a hydrogen atom, and the group A" is a p-phenylene residue which can furthermore carry alkoxy, hydroxyl, phenoxy or acyloxy groups is particularly of interest,

The new dyestuffs are manufactured a) by reacting a dyestuff which contains at least one group of formula -Xl-l, wherein X has the same significance as above, with at least one sulphonylisocyanate which contains at least one group of formula -SO -N=C=O or b) by linking two components of which at least one component contains at least one group of formula -X- -CONRSO by condensation or coupling to give a dyestuff which contains at least one group of formula --XCO-NRSO or (c) by acylation or preferably N-C condensation with the formation of a NC bond) of a compound possessing dyestuff char acter which contains at least one of the groups of formulae -X-CONHSO or -NH-CONR SO with a compound which is preferably an alkylating compound.

Stage c) serves to introduce the groups R and/or R I. Process variant (a) A. Sulphonylisocyanates Possible sulphonylisocyanates for embodiment (a) are optionally substituted aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic sulphonylisocyanates such as for example methyl-sulphonylisocyanate, ethyl-sulphonylisocyanate, isopropyll sulphonylisocyanate, n-propyll -sulphonylisocyanate,

n-butyl- 1 -sulphonylisocyanate, propenl -ylsulphonylisocyanate, n-hexenl -ylsulphonylisocyanate, 4,4-dichlorobutenl -ylsulphonylisocyanate, 2chlorovinylsulphonylisocyanate, cyclohexyll sulphonylisocyanate, cyclohexenl -ylsulphonylisocyanate, 2-chlorethylsulphonylisocyanate, 2-chloropropylsulphonylisocyanate, 2-chlorohexyl- 7 sulphonylisocyanate, 2-methyl-2-chlor0propylsulphonylisocyanate, 2-vinyl-sulphonylisocyanate, phenyl-sulphonylisocyanate, 4.-tolyl-sulphonylisocyanate, 4-chlorophenyl-sulphonylisocyanate, 4-fluorophenylsulphonylisocyanate, 4-bromophenylsulphonylisocyanate, 4-methoxyphenylsulphonylisocyanate, 2,5-dimethyl-phenylsulphonylisocyanate, 3-nitrophenylsulphonylisocyanate, 4-nitrophenyl- 2-methylphenylene-1,4- n-butylenel ,4-bisn-hexylene-l ,6- phenylene-l ,3-bisnaphthalene-1,5-bissulphonylisocyanate,

bis( sulphonylisocyanate), sulphonylisocyanate), bis( sulphonylisocyanate), sulphonylisocyanate),

( sulphonylisocyanate), benzthiazolyl-2- sulphonylisocyanate, thienyl-Z-sulphonylisocyanate and the sulphonyldiisocyanate of formula SO NCO) phenethylsulphonamide, benzenesulphonamide, otoluenesulphonamide, p-toluenesulphonamide, pacetylamino-benzenesulphonamide, 4- bromobenzenesulphonamide, 2-methoxy-4-methyl-5- bromobenzenesulphonamide, lnaphthalenesulphonamide, 2-

S-pyridinesulphonamide, 2-imidazolsulphonamide,

naphthalenesulphonamide, -quinolinesulphonamide,

2-benzimidazolesulphonamide, l ,2,4-triazole-3- sulphonamide, Z-thiazolesulphonamide, 2- benzthiazolesulphonamide, 2-

pyrimidinesulphonamide, 2-pyrazinesulphonamide, 2- nitrofuranesulphonamide and 2-acetylamino-l,3,4- thiadiazole-5-sulphonamide.

B. Dyestuff components The following dyestuffs are for example suitable for use as reactive components which are reacted with the sulphonylisocyanates mentioned in accordance with the invention: 1. A20 dyestuffs C N CHzCHn C N u M CHzCHgOH Calls 0 O OZN -N=N N CHICHI 0 II CHZCHICHI NH:

-C O OCHzCH: OH

-3-(4-hydroxyphenyl)-6- or -7-bromanthraquinone, l,5-dihydroxy-4,8-diamino-2- or -3-( 4'-hydroxy-3- or 2-bromophenyl)anthraquinone and l,5-dihydroxy-4- amino-8-acetoxyethylamino-2- or -3-(4-hydroxyphenyl)-anthraquinone. 3. Nitro dyestuffs HOCHzCHaO-Q-NH-QSOzNH-O mc-O-mr-O-sor-orncmcrrmm I 50 No,

4-Sulphamido-2-nitr0diphenylamino-2'-,3'- or -4- carboxylic acid B-hydroxyethyl ester and 4'-phenylazo- 2-nitro-diphenylamine-4-sulphonic acid N-B- hydroxyethylamide.

4. Styryl dyestuffs N C I CH; O O C CHzCHz O H N C CHzCHz O H C=CH N CH1CHg O H 5. Perinone dyestuffs Mixtures of the dyestuffs of formula or mixtures of the dyestuffs of formula wherein, in each case, one X represents a group of formula -NH and one X represents a hydrogen atom.

C. Reaction conditions The sulphonylisocyanates are, because of their high reactivity, employed in the form of solutions in aqueous inert organic solvents such as methylene chloride, chloroform, carbon tetrachloride, benzene, chlorinated benzenes, chlorinated higher aromatic hydrocarbons,

diethylene, diisopropyl ether, dioxane and acetonitrile. The reaction may take place at room temperature or at higher temperatures. Normally the solution of the sulphonylisocyanate is added slowly to the dyestuff which is to be reacted or to the dyestuff component which is to be reacted. The other conditions for a selective reaction, such as low temperature, optionally below room temperature, and the use of dilute solutions of the reagents, are also observed. if necessary, reactive groups which are present such as hydroxyl or amino groups are protected with suitable protective groups, for example acyl residues, optionally in the presence of catalysts, for example pyridine.

ll. Process variant (b) A. Azo dyestuffs (coupling) The azo dyestuffs according to the invention can also be obtained by coupling a diazonium compound of an amine with a coupling component, with at least one of the components having to contain a group of formula --X-CONRSO R 1. Diazo components Suitable diazo components which contain the group of formula -X--CO-NRSO R are obtained by reaction of an aromatic or heterocyclic nitro compound which possesses at least one group of formula XH, such as for example 2-hydroxy-4-methylsulphonyl-nitrobenzene, 4- hydroxy-2-methylsulphonyl-nitrobenzene or 2,6- dichloro-4-hydroxy-nitrobenzene with a sulphonylisocyanate, an optionally occurring alkylation of the imino group, and subsequent reduction of the nitro group.

As diazo components without groups of formula -X- --CO.NR-SO it is possible to, use the abovementioned diazo components of formula D-NH to the extent that these are not derived from a sulphonylisocyanate.

2. Coupling components Suitable coupling components which contain a group of formula XCO--NR SO are obtained by reaction'of one of the components given below with a sulphonylisocyanate and optional subsequent alkylation: N-B-hydroxyethyl-Nethylaniline, N-B-hydroxyethyl- N-cyanethylaniline, N,N-bis-B-hydroxyethylaniline, 3- acetamino-6-methoxy-N,N-bis-B-hydroxyethylaniline, 3-amino-N,N-bis-B,B-acetoxyethylaniline, 3-amino- N,N-bis-B,;6-cyanethylaniline, l-B-hydroxyethyl-3- methylpyrazolone-( 5), and the B-hydroxyethylamide of 8-hydroxynaphthalene-5- or -6-sulphonic acid.

As coupling components without groups of formula --XCO-NR-SO the following may for example be mentioned: N,B-cyanethyl-N-methylaminobenzene, N,N-di-B hydroxyethylaminobenzene, l-N-B-cyanethyl-N-ethylamino-3-methylbenzene, 3- cyano-2 ,6-dihydroxy-4-methylpyridine, l-N-B- cyanethylamino-3-methylbenzene, l-N,N-di-B- hydroxyethyl-amino-3-thiocyanatobenzene, N-B- cyanethyl-naphthasultam-( l ,8), l-N,N-di-/3cyanethyl- 3-methyl-aminobenzene, N,B-cyanethyl-N,B- hydroxyethyl-aminobenzene, N,B-cyanethyl-2-methylindole, N,B-cyanethyl-tetrahydroquinoline, N-phenylaminobenzene, 4-hydroxy-l -methylquinolone-( 2), l-hydroxy-4-methylbenzene, 2-hydroxy-3-naphtholacid-oanisidide, 8-hydroxyquinoline, 2- naphthylamine-S sulphomethylamide, 1,3- dihydroxybenzene, l-hydroxy-3-cyanomethylbenzene,

l-phenyl-3-methyl-5-pyrazolone and acetoacetic ester.

3. Diazotisation and Coupling The diazotisation of the diazo components mentioned can take place according to methods which are in themselves known, for example with the aid of a mineral acid and sodium nitrite or for example with a solution of nitrosylsulphuric acid in concentrated sulphuric acid.

The coupling can also be carried out in a manner which is in itself known, for example in a neutral to acid medium, optionally in the presence of sodium acetate or similar buffer substances which influence the coupling speed, or of catalysts such as for example dimethylformamide, pyridine or their salts.

The coupling also takes place advantageously if the components are combined by means of a mixing nozzle. This is to be understood as a device in which the liquids to be mixed are combined with one another in a relatively small space, with at least one liquid being passed through a nozzle, preferably at an elevated pressure. The mixing nozzle can for example be constructed, and can operate, according to the principle of water-jet pump, with the feed of one liquid into the mixing nozzle corresponding to the feed of water into the waterpump and the feed of the other liquid into the mixing nozzle corresponding to the connection of the water-jet pump to'the vessel which is to be evacuated, with this latter liquid feed also being allowed to take place at elevated pressure.

Other suitable devices can however also serve for rapid optionally continuous mixing in a small space.

After the coupling reaction has taken place the resulting non-quaternised dyestuffs can easily be separated from the coupling mixture, for example by filtration, since they are practically insoluble in water. If the resulting dyestuffs are quatemised, they are salted out.

B. Styryl dyestuffs (condensation) In order to manufacture the styryl dyestuffs accord ing to the invention, for example an aldehyde of formula wherein c" represents a hydrogen atom or preferably a methyl group and R, and R have the significance given above, can be condensed with a nitrile compound of formula with the application of heat in the presence of a basic catalyst such as for example ammonia, dimethylamine, diethylamine, piperidine, piperidline acetate, sodium alcoholate or potassium alcoholate, optionally in the presence of a solvent such as methanol, ethanol, henzene, toluene, xylene, chloroform or carbon tetrachloride. Suitable nitrile compounds of formula NC-CH- X for the reaction of the styryl dyestuff are for example: malonic acid dinitile, cyanacetic acid methyl es ter, cyanacetic acid ethyl ester, cyanacetic acid butyl ester, cyanacetarnide, cyanacetmethylamide, cyanacetdimethylamide, methylsulphonylacetonitrile and phenylsulphonylacetonitrile. I

, When using solvents thewater produced in the reaction can be continuously removed from the reaction mixture by azeotropic distillaton of these solvents, as a result of which the reaction equilibrium is constantly displaced in favour of the condensation product. The condensation can also take place without a basic catalyst in glacial acetic acid or some other organic acid or in the presence of a solvent by fusing the reagents together in the presence of a basic catalyst, for example ammonium acetate or piperidine acetate.

Anilines which are suitable as starting products are for example obtained by reacting as sulphonylisocyanate with for example 3-methyl-N,N-bis-B-hydroxyethyl-aniline, 3-methyl- N-benzyl-N-,B-hydroxyethyl-amidine, 3-methyl-N- phenoxyethyl-N-B-hydroxyethyl-aniline, 3-methyl-N- B-acetoxyethyl-N-B-hydroxyethyl-aniline, 3-methyl-N- ethyl-N-B-hydroxyethyl-aniline or 7-methyl-N-B- hydroxyethyl-quinoline.

C. Nitro dyestuffs (condensation) In order to manufacture ditro dyestuffs, a sulphonylisocyanate of formula (manufactured by phosgenation of the sulphonamide canbecondensedwith two equivalents of an aniline which is optionally substituted at the aromatic nucleus.

The imino groups of the residues OCON- HSO NH-CO-NH-SO SCO-N- H-SO NR CONHSO and N- H-CONRSO is effected by adding alkylating agents such as for example dimethylsulphate, diethylsulphate, methyl chloride, ethyl bromide, methanesulphonic acid methyl ester or the methyl or ethyl esters of 4-methyl-, 4-chloro-, or 4-nitro-benzenesulphonic acid in suitable organic solvents such as for example xylene, carbon tetrachloride, o-dichloro-benzene, nitrobenzene, dimethylformamide, dimethylsulphoxide, acetonitrile or diox ane, optionally with warming. Further variants of the manufacturing process of sulphonylurethanes according to the invention.

1. Reaction of chlorocarbonic acid esters with alkali salts of sulphonamides or with the free sulphonamides in the presence of alkali carbonate, with at least one of the two organic components having to possess dyestuff character.

2. Reaction of the alkali or alkaline earth salts of sulphonamides which possess dyestuff character with pyrocarbonic acid esters in solution or in suspension up to temperatures of 90C and isolation of the free sulphonylurethanes from the resulting sulphonylurethane salts. 3. Decomposition of sulphonylureas with alcohols possessing dyestuff character.

4. Reaction of sulphochlorides with urethanes, with the sulphochlorides an/or the urethanes possessing dyestuff character.

Quaternisation If the dyestuffs obtained according to the process of the invention and its variants contain quaternisable nitrogen atoms then these can be quatemised subsequent to the manufacture of the dyestuffs. Suitable quaternisable groups are for example those of formulae wherein R and R are alkyl residues which together can form a chain which is optionally interrupted by hetero-atoms, and the group of formula as well as other heterocyclic structures which can be quatemised to cyclammonium groups, such as for example the residues of the above-mentioned heterocyclic diazo components of formula DNH The quaternisation is effected by treatment with esters of strong mineral acids or organic sulphonic acids such as for example dimethylsulphate, diethylsulphate, alkyl halides, such as methyl chloride, methyl bromide or methyl iodide, aralkyl halides, such as benzyl chloride, esters of low molecular alkanesulphonic acids, such as for example the methyl ester of methanesulphonic, ethanesulphonic or butanesulphonic acid and the alkyl esters of 4-methyl-, 4-chloro-or 3- or 4-nitro-)benzenesulphonic acid, which form halogen, sulphuric acid half-ester, alkanesulphonic or benzenesulphonic acid anions as anions, preferably whilst warming in inert organic, solvents, for example xylene, carbon tetrachloride, o-dichlorobenzene and nitrobenzene. It is however also possible to use solvents such as acetic anhydride, dimethylformamide, acetonitrile or dimethylsulphoxide. The quatemised dyestuffs preferably contain, as the anion Y, the residue of a strong acid such as sulphuric acid or its half-esters, or a halide ion, but can also be used as double salts, for example with zinc chloride, or as free bases.

The quatemised dyestuffs for example correspond to the general formulae wherein p is a hydrogen atom, a C -C alkyl group or a negative substituent, and D, A, R R Z Z and Z have the same significance as above.

' Ill. Use

The dyestuffs described above as a rule contain no acid groups which confer solubility in water, especially no sulphonic acid groups, and are therefore sparingly soluble or insoluble in water. If they contain quaternised nitrogen atoms they are on the other hand soluble in water.

The water-insoluble dyestuffs, their mixtures with one another and their mixtures with other azo dyestuffs are, especially after conversion to a finely divided form, for example by grinding, conversion to pastes, reprecipitation etc., excellently suited to the dyeing and printing of synthetic fibres such as for example acrylic or acrylonitrile fibres, polyacrylonitrile fibres and copolymers of acrylonitrile and other vinyl compounds such as acrylic esters, acrylamides, vinylpyridine, vinyl chloride or vinylidene chloride, copolymers of dicyamethylene and vinyl acetate, as well as fibres of acrylonitrile block copolymers, fibres of polyurethanes, polyolefines, cellulose triacetate and 2 /2-acetate, polyamides, such as nylon 6, nylon 6,6 or nylon 12, and especially fibres of aromatic polyesters such as those obtained from therephthalic acid and ethylene glycol or l,4-dimethylolcyclohexane, and copolymers of terephthalic and isophthalic acid and ethylene glycol.

The subject of the present invention is therefore also a process for the dyeing or printing of synthetic fibres, especially of polyester fibres, which is characterised in that dyestuffs which are free of carboxyl and sulphonic acid groups, which contain at least one group of formula -X-CONR-SO wherein R is an acyl group or preferably a hydrogen atom or an optionally substituted alkyl, cycloalkyl, aryl or heterocylcic group and X is an oxygen or sulphur atom or a group of formula NR wherein R is an acyl group or preferably a hydrogen atom or an optionally substituted alkyl, cycloalkyl, aryl or heterocyclic group, their mixtures with one another or their mixtures with other dyestuffs are used.

Preferably, azo dyestuffs,.especially monoazo dyestuffs and disazo dyestuffs, anthraquinones, perinones, styryl dyestuffs and nitro dyestuffs are used.

Amongst the types of fibres, the group of fibres containing ester groups, and above all the polyester fibres, deserve particular emphasis.

For dyeing, the water-insoluble non-quaternised dyestuffs are appropriately used in a finely divided form and dyeing is effected with the addition of dispersing agents such as sulphite cellulose waste lye or synthetic detergents, or a combination of various wetting and dispersing agents. As a rule it is appropriate to convert the dyestuffs to be used, before dyeing, into a dyeing preparation which contains a dispersing agent and finely divided dyestuff in such a form that on dilution of the dyestuff preparations with water a fire dispersion is produced. Such dyestuff preparations can be obtained in a known manner, for example by grinding the dyestuff in a dry or wet form with or without the addition of dispersing agents during the grinding process. The above-mentioned synthetic fibres can also be dyed in organic solvents in which the dyestuff is present as a so lution.

In order to achieve intense dyeings on polyethylene terephthalate fibres it proves appropriate to add a swelling agent to the dyeing bath or to carry out the dyeing process under pressure at temperatures above C, for example at C. Suitable swelling agents are aromatic carboxylic acids, for example benzoic acid or salicylic acid, phenols such as for example 0- or p-hydroxydiphenyl, salicylic acid methyl ester, aromatic halogen compounds such as for example chlorobenzene, o-dichlorobenzene or trichlorobenzene, phenylmethylcarbinol or diphenyl. When dyeing under pressure it proves advantageous to render the dyeing bath weakly acid, for example by adding a weak acid, for example acetic acid.

The non-quaternised water-insoluble dyestuffs to be used in accordance with the invention prove to be particularly suitable for dyeing according to the so-called thermofixing process, according to which the fabric to be dyed is impregnated with an aqueous dispersion of the dyestuff which appropriately contains 1 to 50 percent of urea and a thickener, especially sodium alginate, preferably at temperatures of at most 60C, and is squeezed out in the usual manner. it is appropriate to squeee out in such a way that the impregnated goods retain 50 to 100 percent of their starting weight of dyeing liquor. I

In order to fix the dyestuff, the fabric impregnated in this way is, appropriately after a prior drying, for example in a warm stream of air, heated to temperatures of above 100C, for example between. and 210C.

The thermofixing process which has just been mentioned is of particular interest for dyeing mixed fabrics of polyester fibres and cellulose fibres, especially cotton. In this case the padding liquor contains, in additin to the non-quaternised water-insoluble dyestuff to be used according to the invention, also dyestuffs which are suitable for dyeing cotton, for example direct dyestuffs or vat dyestuffs, or especially so-called reactive dyestuffs, that is to say dyestuffs which can be fixed to the cellulose fibre with the formation of a chemical bond, that is to say for example dyestuffs containing a chlorotriazine or chlorodiazine residue. in the latter case it proves appropriate to add an acid-binding agent, for example an alkali carbonate or alkali phosphate, alkali borate or alkali perborate or their mixtures to the padding solution. When using vat dyestuffs it is necessary for the padded fabric after heat treatment to be treated with an aqueous alkaline solution of a reducing agent which is usual in vat dyeing.

The dyeings on polyester fibres obtained according to the present process are appropriately subjected to a posttreatment, for example by heating with an aqueous solution of a non-ionic detergent.

instead of being applied by impregnation, the dyestuffs specified can, according to the present process, also be applied by printing. For this purpose a printing 19 ink is for example used which in addition to the auxiliary substances usual in printing, such as wetting agents and thickeners, contain the finely dispersed dyestuff optionally mixed with one of the above-mentioned cotton dyestuffs, optionally in the presence of urea and/or an acid-binding reagent.

Using the present process, intense dyeings and prints of excellent fastness properties, especially good fastness to light, sublimation, decatising, washing and chlo- .rine water are obtained. The dyeings on acetate rayon are furthermore distinguished by good gas fastness. A further advantage resides in the good wool and cotton reserve of the dyestuffs to be used in accordance with the process.

The new water-insoluble non-quaternised dyestuffs can also be used for the spin dyeing of polyamides, polyesters and polyolefines. The polymer to be dyed is appropriately mixed, in the form of powders, granules or chips, as a finished spinning solution or in the fused state, with the dyestuff which is introduced in the dry state or in the form of a dispersion or solution in a solvent which may be volatile. After homogeneous distributionof the dyestuff in the solution or melt of the polymer the mixture is processed in a known manner by casting, pressing or extrusion to give fibres, yarns, monofilaments, films and the like.

The new water-soluble quaternised dyestuffs or dyestuff salts are suitable for dyeing and printing the most diverse fully synthetic fibres such as for example polyvinyl chloride, polyamide, polyurethane and especially polyacrylic fibres.

..The new dyestuffs are furthermore also suitable for the bulk colouring of polymerisation products of acrylonitrile, of polyolefines and also of other plastic compositions, and are also suitable for the colouring of oil paints and lacquers. It is also possible to use the abovementioned thermofixing process.

The new water-insoluble non-quaternised dyestuffs in part also represent valuable pigments which can be used for the most diverse pigment applications, for example in a finely divided form for dyeing rayon and viscose or cellulose ethers and esters, for the manufacture of inks, especially of ball pen inks, as well as for the manufacture of coloured lacquers or lacquer-forming substances, solutions and products made of acetylcellulose, nitrocellulose, natural resins or synthetic resins, such as polymerisation resins or condensation resins, for example aminoplasts, alkyd resins, phenoplasts, polyolefines such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, rubber, casein, silicone and silicone resins.

The dyestuffs which are fully methylated at the sulphonylurea or methane group are particularly suitable for dyeing polyolefine fibres such as polypropylene fibres from an aqueous or organic liquor, above all by the padding-thermo-fixing process.

In the examples which follow the arts, unless otherwise specified, denote parts by weight and the percentages denote percentages by weight.

EXAMPLE 1 2.55 parts of 4-[N-ethyl-N-B-hydroxyethyl-amino]-2- methylbenzylidenemalodinitrile, 2.2 parts of ptoluenesulphonylisocyanate and parts by volume of chlorobenzene are heated for 2 /2 hours under reflux. The solvent is distilled off under reduced pressure and the residue is triturated with methanol. The precipitated orange-yellow dyestuff of formula NC CzHs is filtered off, washed with methanol and dried. it dyes polyester fibres from boiling tetrachlorethylene to give greenish-tinged yellow shades.

EXAMPLE 2 4 parts of 4-[N,N-bis-(2-hydroxyethyl)saminol-2- methylbenzylidenemalodinitrile are dissolved in parts by volume of hot chlorobenzene and a solution of 6.6 parts of p-toluenesulphonylisocyanate in 100 parts by volume of chlorobenzene is added dropwise. The mixture is allowed to stand overnight at room temperature. The precipitated dyestuff of formula N(CH1CH1O C ONHOzSO-Ohla) is filtered off, rinsed with a little chlorobenzene and dried. it dyes polyester fibres in boiling tetrachlorethylene to give greenish-tinged yellow shades.

EXAMPLE 3 NC in.

cmcnio CON(CH;) 02sis isolated. It dyes polyester fibres from an aqueous bath to give greenish-tinged yellow shades.

The dyestuffs given in Table 1, corresponding to the formula are obtained in an analogous manner.

TABLE 1 R R R" R1: I Shade on polyesters 1 ON H ""CQHfi Greenish-tinged yellow.

2 CN -H -CHa 3 -CN -H -CHa CH3 Yellow.

4 --ON OCONSO2R -H CHa RI! 5 CN Same as above H i 3 Do.

6.... CN ..do CHa Greenish-tinged yellow.

7 CN d ---CH3 0 D0. 8 --ON do C2H5 Do.

9... CN d0 -H -CH: .10.. CN .-d0 -orn -CH3 Do.

11.... COOO2H5---. -H -H 12... COOC2H5 H -GH3 Same as above Do.

13.. C00C2Hr H -H 14... -CO0C;Hs H T CH: 0 C1 D0.

15... t -H H ".50 CHa 16... Same as above Same as above Do. 17... ...d0.... H3 s do -CH Do.

EXAMPLE 4 p 19.0 parts of N-cyanethyl-N-B-hydroxyethylaniline, 20.0 parts of phenylsulphonylisocyanate and 100 parts by volume of toluene are heated for 3 hours under reflux. After cooling the product which has crystallised out, of formula IHiCN is'filtered off, washed with water and dried. lt dyes polyester fibres from a boiling solution in pure tetrachlorethylene (40 minutes) togive orange shades.

EXAMPLE parts of N-cyanethyl-N-2-( 4'- methylphenylsulphonylaminocarbonyl)- oxyethylaminobenzene, 57 parts of methyl iodide, 50 parts of potassium carbonate and 250 parts by volume of methyl ethyl ketone are boiled for 5 hours under reflux. The reaction mixture is then cooled and the potassium salts are filtered off. The filtrate is evaporated. The slightly yellowish oil is used for the coupling reac tion.

3.5 parts of sodium nitrite are dissolved in 68 parts of sulphuric acid monohydrate. 8.15 parts of lamino- 2-cyano-4-nitrobenzene are introduced at to C and well stirred. After 2 hours the solution is poured into 300 parts of ice water. The diazo solution thus obtained is added to an acetic acid solution of 20.05 parts of the oil obtained according to paragraph 1. The coupling mixture is rendered neutral to Congo Red by means of sodium acetate solution. After completion of the coupling the precipated dyestuff is filtered off, rinsed with water and dried. The dyestuff of formula amoemmmsQ dyes polyester fibres in red shades having excellent 0II2CII1CN fastness properties. RN=NC N/ The dyestuffs of Table 2, which correspond to the Q formula I 10 i y can also be manufactured according to the process described in Example 5.

TABLE 2 R R R Shade on polyester 1.. CH3 Red.

NOZ- "CH3 2M Same as above -I-I 6 Red.

3 d0 CH3 Same as above Orango.

4 d0 H CglI5 Roddish-orango.

5 "do C2H5 Do.

6 do CH; CII3 D0.

7 -CH Red.

NOZ-

8 Same as above C2I'I5 Red.

CII

9 d0 C211 Orangu.

10 .do I-I C H; 11 d0 CH3 CH Yellowish-md.

13. Same as above GI-I Same as above Orange.

14 "d0 -C2H5 DO.

16 .dO 4 a H -CH3 17 d0 CH3 CH3 DO.

| COOCI'I;

R R R Shade on polyester 25..- i 3 Sam; abKZlTj W S OrCH 26 Sameasabove -CH3 ..do Red 27 "d" -C2H5 Red.

28 d0 -CzHs Red.

29... -CH3 Violet. l 411.

EXAMPLE 6 and dyed polyester fibres in red shades. The dyestuff of 0.5 parts of 50 percent strength sodium hydride dispersion are added to a solution of 3.1 parts of the urethane of N-cyanethyl-N-B-hydroxyethyl-aniline and phenylisocyanate (dissolved in 30 parts of dioxane). After 1 hour the sodium salt of the urethane had separated out as a voluminous white precipitate. The sludge was diluted with 50 parts of dioxane and mixed with 1.76 parts of benzenesulphonyl chloride. The mixture was stirred for 2 hours at room temperature, whereuon the white precipitate disappeared and sodium chloride precipitated in a fine form. After filtering and working up, a colourless oil was obtained, which corresponded to the formula CHzCHz C N I cutout 0-o o-N-s 0 The sulphonylurethane of formula CHaCHaC N was obtained in an analogous manner.

1.72 parts of 2-chl0ro-4-nitroaniline were diazotised with nitrosylsulphuric acid and the filtered diazo solution was coupled-with 4.5 parts of the product obtained in the first paraagraph (dissolved in glacial acetic acid: propionic acid, 521). The resulting dyestuff corresponded to the formula CHQCHI U N CHaCHz 0-0 0-1g-s 02-6 formula was manufactured in an analogous manner.

EXAMPLE 7 16.3 parts of 2-cyano-4-nitroaniline are introduced into 183 parts of 1 N nitrosylsulphuric acid. The diazo solution thus obtained is added to a solution of 43.7 parts of N-ethy-N-[Btphenylsulphonyl[methylamino] carbonyl)-B-phenylamino]ethylaminobenzene in 600 parts by volume of ethylene glycol monoethyl ether. The resulting dyestuff of formula is precipitated by pouring out onto ice/water. lt dyes acetate rayon, cellulose triacetate, nylon and polyester fibres in violet shades.

EXAMPLE 8 NOLCgAMFQ precipitates. lt dyes acetate rayon, triacetate, nylon and polyester in red shades.

EXAMPLE 9 The dyestuff of formula was obtained, which dyes polyester fibres in blue shades. The dyestuff of formula JJN IiHCOCHa N-CzH O-C O-N (CH3) S 01051315 was manufactured in an analogous'manner.

EXAMPLE 1O 3-Amino-N,N-bis(B-acetoxyethyU-aniline was dissolved in hot chlorobenzene, mixed with a 20 percent excess of benzenesulphonylisocyanate and stirred for 3 hours at 130 "C. The resulting adduct was boiled for 12 hours under reflux with a threefold excess of methyl iodide, in the presence of dry potassium carbonate, in methyl ethyl ketone. The compound of formula NCH:

was obtained. On coupling with diazotised 2-chloro-4- nitroaniline a dyestuff was obtained which dyed polyester fibres in red shades.

EXAMPLE 1 1 0.5 parts of 50 percent strength sodium hydride dispersion were added to a solution of 3.1 parts of N- cyanethyl-N,B-phenylcarbamylethylaniline in 30 parts by volume of dioxane whilst stirring at room temperature. At 1 hour the sodium salt of the carbamate had separated out as a white voluminous precipitate. 1.72 parts of m-pyridinesulphonyl chloride were added whilst stirring and the mixture was stirred for 3 hours. The precipitated sodium chloride was filtered off. Working up of the dioxane solution yielded a colourless viscous oil of formula CzHaCN The above product was dissolved in glacial acetic acid and coupled with diazotised p-nitroaniline.

A red dyestuff of formula.

CsHs

was produced. If diazotised 2-chloro-4-nitroaniline was used instead of diazotised nitroaniline, a dyestuff was obtained in an analogous manner.

EXAMPLE 12 7.14 parts of 4-(N-ethyl-N,2"-cyanethyl)amino-4'- sulphonamidoazobenzene are dissolved in 20 parts of dimethylformamide. 2.43 parts of triethylamine and 2.86 parts of phenylisocyanate are added and the mixture is stirred for 15 hours at room temperature. Thereafter the reaction mixture is poured onto water, the mixture is rendered acid and the precipitated dyestuff is filtered off; the residue is washed with water and dried.

7.3 parts of the product obtained above are dissolved in 1,200 parts of acetone and mixed with 30 parts of potassium carbonate and 30 parts of methyl iodide. The reaction mixture is heated for 4 hours under reflux. After cooling, the precipitated inorganic salts are filtered off and the filtrate is evaporated. The residue is triturated with water and filtered off. The dyestuff of formula CgH5 EXAMPLE l4 2-( 2-hydroxyethoxy)-4-nitroaniline is diazotised and coupled to N-ethyl-N-(2-cyanethyl)aniline. 11.5 parts of the dyestuff thus obtained are dissolved in 75 parts of chlorobenzene. 8.25 parts of phenylsulphonylisocyanate are added dropwise. The mixture is stirred for 5 hours at 100C and cooled. The precipitated dyestuff I II III IV C H CH3 Orange. NCO 11m 02 s -N=N N l CgHqCN CH:

Same as above CH3 Do. HzNOg S N=N N(C H O C CH3):

. CzHs d0 CH3 D0.

CgH4COOC H 1110; do CH3 Yellow.

EXAMPLE 13 is filtered off, washed with a little chlorobenzene and 9.6 parts of 2,4-dinitro-4-( 2"-hydroxyethoxy)diphenylamine are dissolved in 200 parts of hot chlorobenzene. 8.25 parts of phenylsulphonylisocyanate are added dropwise and the mixture is stirred for a further 8 hours at 100C. The reaction mixture is cooled and the precipitated dyestuff is filtered off, washed with chlorobenzene and dried.

5 parts of the product obtained above are dissolved in 45 parts of acetone and mixed with 20 parts of potassium carbonate and 20 parts of methyl iodide. The reaction mixture is heated for 4 hours under reflux. The inorganic salts are separated off by filtration and the filtrate is evaporated. The residue is then triturated with water and filtered off. The dyestuff of formula is obtained, which dyes polyester fibres in yellow shades of excellent fastness to sublimation.

If the dyestuffs mentioned in column I are reacted with the sulphonylisocyanate mentioned in column II and the resulting product is alkylated with the alkylating agent mentioned in column III, dyestuffs are obtained which dye polyester fibres in the shades given in column IV.

dried.

5.66 parts of the dyestuff condensation product obtained in paragraph 1 are dissolved in parts of acetone. 20 parts of potassium carbonate and 20 parts of methyl iodide are added. The reaction mixture is heated for 4 hours under reflux. The inorganic salts are then filtered off and the filtrate is evaporated. The residue is triturated with water and filtered off. The dyestuff of formula lIiPN oc211.- o corpus- 3 I II III IV Same as above H II I CHaI Yellow. --S OzNC 0 I II III IV 1 02115 on'n 1m.

O2N -NH2 N/ SO2NCO C2H4OH l CQILCN 2 Same as above C2 s RM!- N(C H4OCOCH3)g CH3- -SO9NCO 3 ..d c2115 01m Red.

S02NC0 @s G 4 d0 Same as above..... (lllgl )rnnuu.

CH3 l 5 -dO (|,I-(H3-CH3 ,do Cll l Yellow.

HO-C N 61".? OH d0 01m D0,

HO H4C2() NH2 l 7.... Same as above 0H d0 .7 Cllgl ()rango.

OCI'IB a0 c1131 Do.

I OH HOH4C2O N=N-NH2 EXAMPLE 31 2-Chloro-4-nitroaniline is diazotised and coupled to O'N -N=N C |C cm 'l-( 2-hydroxyethyl)-3-methylpyrazolone. 9.75 parts of the dyestuff thus obtained are dissolved in parts of y 1 hot chlorobenzene. 8.25 parts of phenylsul CHICH2OCONOQS phonylisocyanate are added dropwise and the mixture I is obtained, which dyes polyester fibres and acetate rayon in yellow shades of excellent fastness properties.

Dyestuffs are obtained in an analogous manner if the amines quoted in column I of the table below are diazotised, coupled with the coupling components mentioned in column II, and the resulting dyestuffs acylated with the sulphonylisocyanates mentioned in column Ill and subsequently alkylated with the alkylating agents mentioned in column lV. Dyestuffs which dye polyester fibres in the shades mentioned in column V are obtained.

4.57 parts of 4-aminophenacyltrimethylammonium chloride are dissolved in 20 parts of water and 7 parts by volume of concentrated hydrochloric acid are added. The solution is diazotised at to C by adding I II III IV v 1.... HC--C-CH3 oHn Yellow.

B 0000 NHZ II II Os OzNCO C2H4OH 2 Same as above CzH5I Do.

omo0o-ONH2 7 H- -s OzNCO 3...- I HC--C-C H3 C1111 Do.

OzN- NH2 ll I! -s O'ANC o HO-C /N 4.. ON Hfi-(IT-CHQ Same as above CIIiI Orange.

I H2N-C OzN NH2 C2H40H EXAMPLE 16 25 is filtered off and dried. It dyespolyacrylonitrile fibres in orange shades of excellent fastness properties.

If the amines mentioned in column I in the table below are diazotised and coupled as above with the coupling components mentioned in column ll, dye- 5 parts by volume of 4 N sodium nitrite solution. The 3 stuffs are b which dye acrylic fibres and the diazo solution is added at 0 to 5C to a solution of 7.74 Shades mentloned In column I 11 Ill 6) CQHqCN Scarlet. Cl(CH3)aNOH2CO-NH2 N ogHloo ONO2S-CH3 CH3 can Same as above CQI'LC O O C2I'I5 [)o.

CzH4OCONO2S CZH4CN Do. OzN- NH2 602113 16 \C2H4OCOITIO:S 01 cm 63 Same as above Orange. C1 (CH3)3N(CHz)aHN02S -NH2 parts of N-cyanethyl-N-2'( phenylsulphonyHme- EXAMPLE l7 thylamimlcarbmyn'mfi 'hydroxyethylaminoben' 7.6 parts of sodium nitrite are sprinkled at 0 to 10C f T fi gfi 22 3 i ggg g git g f 3 9;; into 90 parts of concentrated sulphuric acid, the mix 3 ffeis fii r 5. d g hot a and ture is the heated to 65C until everything has dissolved yes u fl 0 l l Th and is then cooled to 0C, and 100* parts by volume of salted a ra s i? ter the so 6 a mixture of glacial acetic acid and propionic acid, in pump] a 6 yes u 0 a the ratio of 6:1, are added dropwise. 19.4 parts of 6- a; ethoxy-Z-aminobenzthiazole, dissolved in 100 parts by Cl (CH3)3N*-CH2 0'O volume of a mixture of glacial acetic acid and propionic Y acid (6: 1) are added dropwise to the resulting solution CZHCN and the reaction mixture is stirred for a further 3 hours at 0 to 5C. 7.5 parts of urea are then added in portions to this diazo solution. The diazo solution thus obtained 011140001 0 is added, at 0 to 5C, to a solution of 38.7 parts of N- JHa cyanethyl-N-2( phenylsulphonyl- A [methylamino]carbonyl)-oxyethylaminobenzene in 150 parts of acetone. The coupling mixture is rendered neutral to Congo Red by means of sodium acetate solution. After completion of the coupling the solution is filtered and the dyestuff is washed with water and dried.

8.9 parts of the dyestuff obtained above are dissolved in 150 parts of warm chlorobenzene. A solution of 2.85 parts of dimethylsulphate in 20 parts of chlorobenzene is added dropwise and the reaction mixture is stirred for a further 4 hours at 95 to 100C. The mixture is then cooled and filtered. The filter cake is dissolved in hot water and filtered to clarify the solution. The filtrate is salted out. The precipitated dyestuff of formula CZHlCN I acrylic fibres in the shades given in column IV.

EXAMPLE 18 A mixture of 6.8 parts of l-amino-4-ptoluenesulphonylamino-2-( ,B-hydroxyethyUoxyanthraquinone, 6 parts of p-toluenesulphonylisocyanate and 200 parts of toluene is stirred for 7 hours at room temperature and the dyestuff of formula ocrncmo o ormsm-Gm ocmcnio 0 01 1s 0 ,Q-cn:

( i NH-SOz-O-CH;

and dyes polyester fibres in reddish-orange shades.

EXAMPLE 19 A mixture of 6.8 parts of l-amino-4-hydroxy-2-( B- hydroxyethyl)oxyanthraquinone and 4 parts of p- III IV CzHs 4 H3 CzH4OCOIIOgS-O Dimethylsulfatn.. Blue.

N /C2II4CN d0 Violet.

C-NH C H4OCONOgS- -CH3 S 3113 HN-CNH2 C2H4CN .d0 Rod.

N C2H4OCONO2S N\ /C2H4CN d0 Red.

. C mm \s f Ha Same as abo NH2 ve do Violet N N H N N d0 do I) a n Il3C (J-NII toluenesulphonylisocyanate in 150 parts of chlorobenzene was stirred for 7 hours at room temperature. Working up yielded 50 parts of an orange powder which represents the dyestuff of formula 24.8 parts of the sulphonylurethane obtained above, 34 parts of anhydrous potassium carbonate, 31 parts of dimethylsulphate and 1,500 parts of acetone are boiled for hours under reflux. After working up 25 parts of the methylated product were obtained as a violet powder which corresponds to the formula and dyes polyester fibres in bluish-tinged red shades.

EXAMPLE 20 A mixture of 12.5 parts of 1-methylamino-4- aminoanthraquinone, 18 parts of benzenesulphonylisocyanate and 1 part of pyridine in 150 parts of toluene is boiled under reflux for 3 hours. After cooling 2l parts of a light green powder precipitate, which corresponds to the formula 0 NH CH;

o NHoo-NH-sozO and dyes polyester fibres in violetshades.

If 25 parts of p-toluenesulphonylisocyanate were used instead of the benzenesulphonylisocyanate, 25 parts of a p-toluenesulphonylurea of formula 0 NH'oHi d NHCONHBOa-O were obtained, which dyes polyester fibres in violet shades.

1f the dyestuff obtained in the first paragraph parts) was boiled with 113 parts of dimethylsulphate and parts of anhydrous potassium carbonate in 1,000 parts of acetone under reflux for 12 hours, a blue powder was obtained which corresponds to the formula O NECHa and dyes polyester fibres in violet shades.

EXAMPLE 21 A mixture of 24 parts of 1-amino-4- hydroxyanthraquinone, 1 part of pyridine, 18 parts of benzenesulphonylisocyanate and 1,500 parts of toluene is boiled for 3 hours under reflux. After cooling 40 parts of a reddish-orange powder are isolated, which corresponds to the formula I HCQNHSOz-O and dyes polyester fibres in orange shades.

If this dyestuff is methylated, a valuable dyestuff o isothiazoleanthrone, 0.5 parts of pyridine, 18 parts of benzenesulphonylisocyanate and 200 parts of toluene is heated for 4 hours under refulx. After cooling 22 parts of a yellow powder are isolated, which corresponds to the formula l 0 NHCO-NHSOa-Q and dyes polyester fibres in yellow shades.

The compound of formula which dyes polyester fibres in yellow shades, is manufactured in an analogous manner. 

1. A DYESTUFF WHICH IS FREE FROM SULFONIC ACID GROUPS AND WHICH HAS
 2. A dyestuff of claim 1 of the formula: 